A new strategy for PET depolymerization: Application of bimetallic MOF-74 as a selective catalyst.

Large-volume production of poly(ethylene terephthalate) (PET), especially in the form of bottles and food packaging containers, causes problems with polymer waste management. Waste PET could be recycled thermally, mechanically or chemically and the last method allows to obtain individual monomers, but most often it is carried out in the presence of homogeneous catalysts, that are difficult to separate and reuse. In view of this, this work reports for the first time, application of bimetallic MOF-74 - as heterogeneous catalyst - for depolymerization of PET with high monomer (bishydroxyethyl terephthalate, BHET) recovery. The effect of type and amount of second metal in the MOF-74 (Mg/M) was systematically investigated. The results showed increased activity of MOF-74 (Mg/M) containing Co2+, Zn2+ and Mn2+ as a second metal, while the opposite correlation was observed for Cu2+ and Ni2+. It was found that the highest catalytic activity was demonstrated by the introduction of Mg-Mn into MOF-74 with ratio molar 1:1, which resulted in complete depolymerization of PET and 91.8% BHET yield within 4 h. Furthermore, the obtained catalyst showed good stability in 5 reaction cycles and allowed to achieve high-purity BHET, which was confirmed by HPLC analysis. The as-prepared MOF-74 (Mg/Mn) was easy to separate from the post-reaction mixture, clean and reuse in the next depolymerization reaction.

Morphology control through the synthesis of metal-organic frameworks.

Designable morphology and predictable properties are the most challenging goals in material engineering. Features such as shape, size, porosity, agglomeration ratio significantly affect the final properties of metal-organic frameworks (MOFs) and can be regulated throughout synthesis parameters but require a deep understanding of the mechanisms of MOFs formation. Herein, we systematically summarize the effects of the individual synthesis factors, such as pH of reaction mixture, including acidic or basic character of modulators, temperature, solvents types, surfactants type and content and ionic liquids on the morphology of growing MOFs. We identified main mechanisms of MOFs' growth leading to different morphology of final particles and next systematically discuss the effect of miscellaneous parameters on MOFs morphology based on the main mechanisms related to the nucleation, growth and formation of final MOFs structure, including coordination modulation, protonation/deprotonation acting and modulation by surfactants or capping agents. The effect of microwaves and ultrasound employment during synthesis is also considered due to their affecting especially nucleation and particles growing steps during MOFs formation.